5-(pyrazol-1-1-yl)-benzoic acid thiol esters with herbicidal action

ABSTRACT

Novel 5-(pyrazol-1-yl)-benzoic acid-thiolesters of the formula I have good selective-herbicidal action in pre- and postemergent application. They also inhibit plant growth. The esters correspond to formula I ##STR1## wherein X is hydrogen, halogen or C 1  -C 4  alkyl 
     Y is C 1  -C 4  alkyl or 
     X and Y together with the carbon atoms, to which they are bound, form a 5- to 6-membered ring, which can be substituted by methyl, 
     Z is halogen, C 1  -C 6  alkyl, C 1  -C 4  alkoxy or C 1  -C 4  alkylthio 
     R 1  is hydrogen or halogen 
     R 2  is halogen 
     A-Q together are hydroxyl or a radical --CH(COOR 3 )COOR 4   
     A is a C 1  -C 4  alkylene bridge 
     Q, R 3  and R 4  have the meaning given in the disclosure. 
     The disclosure contains methods for synthesizing these esters and examples showing their use.

This is a divisional of application Ser. No. 361,188 filed on June 5,1989, now U.S. Pat. No. 4,946,492.

The present invention relates to novel 5-(pyrazol-1-yl)benzoic acidthiol esters of formula I with herbicidal and plant growth regulatingproperties, and to the preparation of these novel esters. The inventionalso relates to compositions which contain said novel compounds and tothe use thereof for selectively controlling weeds or for regulatingplant growth.

The novel 5-(pyrazol-1-yl)benzoic acid thiol esters are of formula I##STR2## wherein X hydrogen or halogen,

Y is C₁ -C₄ alkyl,

X and Y together with the carbon atoms, to which they are bound formalso a 5- to 6-membered ring, which can be substituted by methyl,

Z Halogen, C₁ -C₆ alkyl, C₁ -C₄ alkoxy or C₁ -C₄ alkylthio,

R₁ is hydrogen or halogen,

R₂ is halogen,

A-Q taken together is hydrogen or a radical --CH(COCH₃)COOR₄,

A is a straight chain or branched C₁ -C₄ alkylene bridge, which isunsubstituted or mono- or polysubstituted by C₁ -C₄ alkoxy, C₁ -C₄alkylthio or cyano,

Q is hydroxyl, halogen, cyano, thiocyanato (--SCN), C₂ -C₆ alkenyl, C₂-C₆ haloalkenyl, C₂ -C₆ cyanoalkenyl, C₂ -C₄ alkynyl, or a radical--C(R₃)=CH--COOR₄, --CH[N(R₃)₂ ]COOR₃, --NR₅ R₆, --CONR₇ R₈, --Si(R₁₁)₃,--COOCH₂ Si(CH₃)₂ C₁ -C₆ alkyl, --COON=C(R₉)₂, --C(R₃)=(OR₁₀)₂,--PO(OR₁₂)--(O)_(p) R₁₂, --CON(R₁₃)SO₂ C₁ -C₆ alkyl, --CON(R₁₃)SO₂ C₁-C₄ haloalkyl, C₁ -C₆ alkylcarbonyl, C₁ -C₆ alkoxycarbonyl, a radicalbenzoyl or benzylcarbonyl whose phenyl ring is unsubstituted, mono- orpolysubstituted by halogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄alkoxy, C₁ -C₄ haloalkoxy, cyano or nitro, Q is further a radicalCOOR₁₄, --CON(R₃)CH₂ C(OC₁ -C₆ alkyl)₂ or C₁ -C₈ alkanoyloxy,

p is zero or 1,

R₃ is hydrogen, C₁ -C₆ alkyl or C₂ -C₆ alkoxyalkyl,

R₄ is C₁ -C₆ alkyl or C₁ -C₆ hydroxyalkyl,

R₄ and R₅ are independently of each other hydrogen, C₁ -C₆ alkyl, C₂ -C₆alkoxyalkyl, C₃ -C₆ alkenyl, C₃ -C₆ alkynyl or C₃ -C₆ cycloalkyl,2-furanylmethyl, 2-tetrahydrofuranylmethyl,2-(5-methyl)-tetrahydrofuranylmethyl or 2-thienylmethyl

R₅ and R₆ form together with the nitrogen atom, to which they are boundalso a radical pyrrolidino, piperidino oder morpholino,

R₇ and R₈ are independently of each other hydrogen, C₁ -C₁₂ alkyl, C₃-C₈ alkenyl, C₃ -C₆ alkynyl, C₂ -C₈ alkoxyalkyl, benzyl, phenyl or C₁-C₄ cyanoalkyl,

R₇ and R₈ form together with the nitrogen atom, to which they are bounda radical pyrrolidino, piperidino, morpholino, thiomorpholino,4-methylpiperazino, pyrazolidino, imidazolidino or 1,2,4-triazol, whichis unsubstituted or mono- or disubstituted by C₁ -C₄ alkyl,

R₉ is C₁ -C₆ alkyl or two adjacent R₉ can form a C₂ -C₆ alkylene bridge,

R₁₀ is C₁ -C₄ alkyl or C₁ -C₄ haloalkyl or two adjacent R₁₀ from a1,2-ethylene-, 1,3-propylene- or 1,2-cyclohexylene bridge,

R₁₁ is C₁ -C₆ alkyl or C₁ -C₆ alkoxy,

R₁₂ is hydrogen, C₁ -C₆ alkyl, C₂ -C₆ alkenyl or C₃ -C₆ alkynyl or C₃-C₇ -cycloalkyl,

R₁₃ is C₁ -C₄ alkyl, or C₃ -C₇ cycloalkyl and

R₁₄ is hydrogen, C₁ -C₁₂ alkyl, C₁ -C₆ alkoxyalkyl, C₃ -C₇ alkenyl, C₃-C₆ cyclo-alkyl, C₃ -C₅ alkenyloxy-C₁ -C₄ alkyl, C₁ -C₆ alkylthio-C₁ -C₄alkyl or C₁ -C₄ dialkylamino-C₁ -C₄ alkyl

Similar tetrahydrophthalimido-N-benzoic acid esters are described in thepublished European Patent applications EP-A 207,894 and 233,151. Thethiolesters of this invention are structurally different and aredistinguished from those by a more specific selective-herbicidalactivity against grasses and weeds in cultures of cultivated plants.

Particularly active compounds are those of the formulae below, wherein Qhas one of the following significances: ##STR3## wherein A, R₁, R₂, X, Yand Z have the meaning given above; ##STR4## wherein A, R₁, R₂, X, Y andZ have the meaning given above and Hal is a halogen atom; ##STR5##wherein A, R₁, R₂, X, Y and Z have the meaning given above; ##STR6##wherein A, R₁, R₂, X, Y and Z have the meaning given above; ##STR7##wherein A, R₁, R₂ the R₃ independently of each other, X, Y and Z havethe meaning given above; ##STR8## wherein A, R₁, R₂, R₅, R₆, X, Y and Zhave the meaning given above; ##STR9## wherein A, R₁, R₂, R₇, R₈, X, Yand Z have the meaning given above; ##STR10## wherein A, R₁, R₂, X, Yand Z have the meaning given above; ##STR11## wherein A, R₁, R₂, R₉, X,Y and Z have the meaning given above; ##STR12## wherein A, R₁, R₂, R₃,R₄, X, Y and Z have the meaning given above; ##STR13## wherein A, R₁,R₂, R₃, R₁₀, X, Y and Z have the meaning given above; ##STR14## whereinA, R₁, R₂, R₁₁, X, Y and Z have the meaning given above; ##STR15##wherein A, p, R₁, R₂, R₁₂, X, Y and Z have the meaning given above;##STR16## wherein A, R₁, R₂, R₁₃, X, Y and Z have the meaning givenabove; ##STR17## wherein A, R₁, R₂, R₁₃, X, Y and Z have the meaninggiven above; ##STR18## wherein A, R₁, R₂, X, Y and Z have the meaninggiven above; ##STR19## wherein A, R₁, R₂, X, Y and Z have the meaninggiven above; ##STR20## wherein A, R₁, R₂, R₁₄, X, Y and Z have themeaning given above; ##STR21## wherein A, R₁, R₂, X, Y and Z have themeaning given above.

The invention comprises also the possible optically active isomers,diastereomers and enantiomers and their mixtures, in which the5-(N-3,4,5,6-tetrahydrophthalimido)benzoic-acid-thiol-esters of formulaI may occur.

In the above definitions the expression halogen includes fluorine,chlorine, bromine or fluorine, especially fluorine, chlorine andbromine.

The expression alkyl, taken by itself or as part of a substituentincludes straight-chained or branched radicals. Examples therefore aremethyl, ethyl, n-propyl, isopropyl, n-butyl, sec. butyl, tert. butyl,isobutyl as well as the higher homologs thereof, pentyl, hexyl, heptyl,octyl, etc. together with their isomers. Cyanoalkyl radicals containsaccordingly an additional carbon atom.

The C₂ -C₆ alkenyl- or C₂ -C₆ alkynyl radicals mentioned in the abovedefinition include also straight-chained and branched radicals. Alkenylincludes especially 2-propenyl (allyl), 2-methyl-2-propenyl (methallyl),1-methyl-2-propenyl, 2-butenyl and 3-butenyl, and alkynyl are preferably2-propinyl (propargyl), 2-butinyl and 3-butinyl radicals. The alkenylradicals of the definitions of Q, R₆ and R₇ are preferably allyl,methallyl or 2-butenyl and preferred alkynyl radicals are propargyl and2-butynyl. If these unsaturated radicals are bound via an oxygen atom tothe rest of the molecule, the radical is bound preferably via asaturated carbon atom to the oxygen.

The definition A includes methylene, 1,2-ethylene and 1,3-propylen aswell as radicals which can be derived therefrom by substitution of oneto two hydrogen atoms, such as 1,1-ethylene, isopropylene(2,2-propylene), 1,2-propylene, 2,3-butylene and1,1-dimethyl-1,2-ethylene, 1,2-butylene, 1,3-butylene. Preferredradicals A are methylene, 1,2-ethylene, 1,2-propylene, and 2,3-butylene.

The generic definitions given in other substituents of the compounds offormula I comprise e.g. the following single radicals, which enumerationis not limiting the invention:

Haloalkyls are alkyl radicals which are partly or completely halogenatedwith identical or different halogen atoms and which correspond to thegiven range of the definition, such as e.g. trifluoromethyl,trichloromethyl, difluoromethyl, dichloromethyl, 2,2,2-trifluoroethyland 1,1,1,3,3,3-hexafluoroprop-2-yl.

Alkoxy are to be understood radicals in the given range of thedefinition, such as preferably methoxy and ethoxy. C₁ -C₄ Alkoxy-C₂ -C₄alkyl and C₁ -C₄ haloalkoxy in the given range of the definition arealso to be understood as alkoxy radicals, such as e.g. methoxymethyl,methoxyethyl, difluoromethoxy, dichloromethoxy, trifluoromethoxy,chlorodifluoromethoxy and trichloromethoxy.

In the substituents, which consist of several basic elements, the partscan be chosen freely within the given range of the definition.

In accordance with the present invention, the novel5-(pyrazol-1-yl)-benzoic acid thiol esters of formula I are prepared byreacting a 5-(pyrazol-1-yl)benzoic acid of the formula II ##STR22##wherein R₁, R₂, X, Y and Z have the above given meaning, with a stronghalogenating agent, to form the corresponding acid-halide of the formulaIII ##STR23## wherein R₁, R₂, X, Y and Z have the above given meaning,and Hal is a halogen atom, the acid halide is then converted in an inertorganic solvent, in the presence of at least the equimolar amount of abase, with a mercaptan of the formula IV

    HS--A--Q                                                   (IV)

wherein

A and Q have the meaning given above to 5-(pyrazol-1-yl)benzoicacid-thiol ester of the formula I;

or by treating the acid-halide of the formula III in an inert organicsolvent, in the presence of a base with hydrogen sulfide, to form the5-(pyrazol-1-yl)thiolbenzoic acid of the formula V ##STR24## wherein R₁,R₂, X, Y and Z have the meaning given above, and converting this acid inan inert organic solvent, in the presence of the equimolar amount of abase, with an alkylhalide of the formula VI

    Hal--A--Q                                                  (VI)

wherein

A and Q have the meaning given above and Hal is a halogen atom,preferably chlorine or bromine to a 5-(pyrazol-1-yl)-benzoicacid-thiolester of the formula I.

Another way to prepare the 5-(pyrazol-1-yl)benzoic acid-thiol esters offormula I consists in nitrating a 5-(pyrazol-1-yl)-benzoic acid of theformula VII ##STR25## wherein R₁, X, Y and Z have the meaning givenabove, with a mixture of concentrated nitric acid and concentratedsulfuric acid, to obtain a 2-nitro-5-(pyrazol-1-yl)-benzoic acid of theformula VIII ##STR26## wherein R₁, X, Y and Z have the meaning givenabove, and reducing this nitrobenzoic acid in a way known per se bymeans of hydrogen to the 2-amino-5-(pyrazol-1-yl)-benzoic acid of theformula IX ##STR27## wherein R₁, X, Y and Z have the meaning givenabove, and diazotizing this aminobenzoic acid, in aqueous-acid medium,with sodium nitrate and a copper I-compound of the formula X

    Cu.sup.I -Hal                                              (X)

wherein Hal is chlorine, bromine or iodine, to the5-(pyrazol-1-yl)-benzoic acid derivative of the formula II, which isthen treated with a strong halogenating agent, as in the previous methodto form the benzoic acid-halide of the formula III, which is furtherconverted either directly or via the 5-(pyrazol-1-yl)-thiolbenzoic acidof the formula V, to the 5-(pyrazol-1-yl)-benzoic acid-thiolester of theformula I.

Suitable solvents or diluents for this reaction are higher boilinghydrocarbons, lower alkane acids and the esters thereof, higher boilingketones and ethers. Examples of such solvents and diluents are toluene,xylene, acetic acid, ethyl acetate, isopropyl ether, tetrahydrofuran andmethyl ethyl ketone.

The reaction takes place at a temperature in the range from 0° C. to theboiling point of the reaction mixture.

The reaction conditions in all described variants are similar.

The compounds of formula I are usually successfully applied atconcentrations of 0.05 to 4 kg/ha, in particular 0.1 to 1 kg/ha.

When used at low rates of application, the compounds of formula I havegood selective growth inhibiting and selective herbicidal propertieswhich make them most suitable for use in crops of useful plants,preferably in cereals, cotton, maize and rice, especially however insoybeans. In some cases damage is also caused to weeds which have onlybeen controlled up to now with total herbicides.

The mode of action of these compounds is unusual. Many aretranslocatable, i.e. they are absorbed by the plant and transported toother parts of it where they then exert their action. Thus, for example,it is possible to damage perennial weeds to the roots by surfacetreatment. Compared with other herbicides and growth regulators, thenovel compounds of formula I are effective even when used at very lowrates of application.

The compounds of formula I have in addition pronounced plant growthinhibiting properties. The growth of both monocots and dicots isinhibited.

Thus, for example, the compounds of formula I selectively inhibit thegrowth of leguminosae which are frequently planted as cover crops intropical regions, so that, while soil erosion between cultivated plantsis prevented, the cover crops cannot compete with the cultivated plants.

Inhibition of the vegetative growth of many cultivated plants permitsmore plants to be sown in a crop area, so that a higher yield may beobtained per unit of area. A further mechanism of yield increase usinggrowth inhibitors resides in the fact that nutrients are ableincreasingly to promote flower formation and fruiting, whereasvegetative growth is inhibited.

The compounds of formula I can also be used for defoliating anddesiccating crops of cotton and potatoes. By treating the crops at themoment of ripening, the harvesting of the cotton capsules or of thetubers is greatly facilitated when the leaves fall off and/or shrivel upor when the shrubs shrivel up.

At higher rates of application of compounds of formula I, all testedplants are so severely damaged in their development that they die.

The invention also relates to herbicidal and plant growth regulatingcompositions which contain a novel compound of formula I, and also tomethods of controlling weeds pre- and postemergence and of inhibitingthe growth of monocots and dicots, especially grasses, tropical covercrops and tobacco plant suckers.

The compounds of formula I are used in unmodified form or, preferably,together with the adjuvants conventionally employed in the art offormulation, and are therefore formulated in known manner e.g. toemulsifiable concentrates, directly sprayable or dilutable solutions,dilute emulsions, wettable powders, soluble powders, dusts, granulates,and also encapsulations in e.g. polymer substances. As with the natureof the compositions, the methods of application, such as spraying,atomising, dusting, scattering or pouring, are chosen in accordance withthe intended objectives and the prevailing circumstances.

The formulations, i.e. the compositions, preparations or mixturescontaining the compound (active ingredient) of formula I and, whereappropriate, a solid or liquid adjuvant, are prepared in known manner,e.g. by homogeneously mixing and/or grinding the active ingredients withextenders, e.g. solvents, solid carriers and, where appropriate,surface-active compounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractionscontaining 8 to 12 carbon atoms, e.g. xylene mixtures or substitutednaphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate,aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols andglycols and their ethers and esters, such as ethanol, ethylene glycol,ethylene glycol monomethyl or monoethyl ether, ketones such ascyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone,dimethyl sulfoxide or dimethylformamide, as well as vegetable oils orepoxidised vegetable oils such as epoxidised coconut oil or soybean oil;or water.

The solid carriers used e.g. for dusts and dispersible powders arenormally natural mineral fillers such as calcite, talcum, kaolin,montmorillonite or attapulgite. In order to improve the physicalproperties it is also possible to add highly dispersed silicic acid orhighly dispersed absorbent polymers. Suitable granulated adsorptivecarriers are porous types, for example pumice, broken brick, sepioliteor bentonite; and suitable nonsorbent carriers are materials such ascalcite or sand. In addition, a great number of pregranulated materialsof inorganic or organic nature can be used, e.g. especially dolomite orpulverised plant residues.

Depending on the nature of the compound of formula I to be formulated,suitable surface-active compounds are non-ionic, cationic and/or anionicsurfactants having good emulsifying, dispersing and wetting properties.The term "surfactants" will also be understood as comprising mixtures ofsurfactants.

Suitable anionic surfactants can be both water-soluble soaps andwater-soluble synthetic surface-active compounds.

Suitable soaps are the alkali metal salts, alkaline earth metal salts orunsubstituted or substituted ammonium salts of higher fatty acids (C₁₀-C₂₂), e.g. the sodium or potassium salts of oleic or stearic acid, orof natural fatty acid mixtures which can be obtained e.g. from coconutoil or tallow oil. Mention may also be made of fatty acid methyltaurinsalts.

More frequently, however, so-called synthetic surfactants are used,especially fatty sulfonates, fatty sulfates, sulfonated benzimidazolederivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are usually in the form of alkali metalsalts, alkaline earth metal salts or unsubstitued or substitutedammonium salts and contain a C₈ -C₂₂ alkyl radical which also includesthe alkyl moiety of acyl radicals, e.g. the sodium or calcium salt oflignosulfonic acid, of dodecylsulfate or of a mixture of fatty alcoholsulfates obtained from natural fatty acids. These compounds alsocomprise the salts of sulfuric acid esters and sulfonic acids of fattyalcohol/ethylene oxide adducts. The sulfonated benzimidazole derivativespreferably contain 2 sulfonic acid groups and one fatty acid radicalcontaining 8 to 22 carbon atoms. Examples of alkylarylsulfonates are thesodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid,dibutylnaphthalenesulfonic acid, or of a naphthalenesulfonicacid/formaldehyde condensation product.

Also suitable are corresponding phosphates, e.g. salts of the phosphoricacid ester of an adduct of p-nonylphenol with 4 to 14 moles of ethyleneoxide, or phospholipids.

Non-ionic surfactants are preferably polyglycol ether derivatives ofaliphatic or cycloaliphatic alcohols, or saturated or unsaturated fattyacids and alkylphenols, said derivatives containing 3 to 10 glycol ethergroups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moietyand 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.

Further suitable non-ionic surfactants are the water-soluble adducts ofpolyethylene oxide with polypropylene glycol,ethylenediaminopolypropylene glycol and alkylpolypropylene glycolcontaining 1 to 10 carbon atoms in the alkyl chain, which adductscontain 20 to 250 ethylene glycol ether groups and 10 to 100 propyleneglycol ether groups. These compounds usually contain 1 to 5 ethyleneglycol units per propylene glycol unit.

Representative examples of non-ionic surfactants arenonylphenolpolyethoxyethanols, castor oil polyglycol ethers,polypropylene/polyethylene oxide adducts,tributylphenoxypolyethoxyethanol, polyethylene glycol andoctylphenoxypolyethoxyethanol.

Fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylenesorbitan trioleate, are also suitable non-ionic surfactants.

Cationic surfactants are preferably quaternary ammonium salts whichcontain, as N-substituent, at least one C₈ -C₂₂ alkyl radical and, asfurther substituents, unsubstituted or halogenated lower alkyl, benzylor hydroxy-lower alkyl radicals. The salts are preferably in the form ofhalides, methylsulfates or ethylsulfates, e.g. stearyltrimethylammoniumchloride or benzyldi(2-chloroethyl)ethylammonium bromide.

The surfactants customarily employed in the art of formulation aredescribed e.g. in the following publications:

"McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp.,Ridgewood, N.J. 1981; H. Stache, "Tensid-Taschenbuch" (Handbook ofSurfactants), C. Hanser Verlag, Munich & Vienna, 1981.

The herbicidal preparations usually contain 0.1 to 95%, preferably 0.1to 80%, of a compound of formula I, 1 to 99.9% of a solid or liquidadjuvant, and 0 to 25%, preferably 0.1 to 25%, of a surfactant.

Preferred formulations are composed in particular of the followingconstituents (%=percentage by weight):

    ______________________________________                                        Emulsifiable concentrates                                                     ______________________________________                                        compound of formula I:                                                                        1 to 20% preferably 5 to 10%                                  surfactant:     5 to 30%, preferably 10 to 20%                                liquid carrier: 50 to 94%, preferably 70 to 85%                               ______________________________________                                    

    ______________________________________                                        Dusts                                                                         ______________________________________                                        compound of formula I:                                                                       0.1 to 10%, preferably 0.1 to 1%                               solid carrier: 99.9 to 90%, preferably 99.9 to 99%                            ______________________________________                                    

    ______________________________________                                        Suspension concentrates                                                       ______________________________________                                        compound of formula I:                                                                        5 to 75%, preferably 10 to 50%                                water:          94 to 25%, preferably 90 to 30%                               surfactant:     1 to 40%, preferably 2 to 30%                                 ______________________________________                                    

    ______________________________________                                        Wettable powders                                                              ______________________________________                                        compound of formula I:                                                                        0.5 to 90%, preferably 1 to 80%                               surfactant:     0.5 to 20%, preferably 1 to 15%                               solid carrier:  5 to 95%, preferably 15 to 90%                                ______________________________________                                    

    ______________________________________                                        Granulates                                                                    ______________________________________                                        compound of formula I:                                                                       0.5 to 30%, preferably 3 to 15%                                solid carrier: 99.5 to 70%, preferably 97 to 85%.                             ______________________________________                                    

Whereas commercial products will be preferably formulated asconcentrates, the end user will normally employ dilute formulations. Theformulations can be diluted to a concentration as low as 0.001% ofactive ingredient. The rates of application are usually from 0.005 to 5kg a.i./ha.

The compositions may also contain further ingredients such asstabilisers, antifoams, viscosity regulators, binders, tackifiers, aswell as fertilisers and other compounds for obtaining special effects.

The following Example illustrates the preparation of a compound of theformula I. Further compounds prepared in corresponding manner are listedin the subsequent Tables. Temperatures are given in degrees centigrade,pressures in millibar (mbar).

EXAMPLE 1 Preparation of5-[2-(3-chloro-4,5,6,7-tetrahydro-2H-indazolyl)]-2-chloro-4-fluorobenzoicacid-(methoxy carbonylmethylthiol)ester ##STR28##

A solution of 3.5 g of5-[2-(3-chloro-4,5,6,7-tetrahydro-2H-indazolyl)]-2-chloro-4-fluorobenzoicacid chloride in 30 ml of toluene is added slowly, while stirring atroom temperature, to a mixture of 1.1 g of thioglycolic acid-methylester and 1.5 ml of triethylamine in 50 ml of toluene. After everythingis added, the reaction mixture is stirred for another 3 hours at roomtemperature. The triethylamine-hydrochloride is then filtered off, thefiltrate is concentrated under vacuum. The residue is the title productwhich melts at 98°-99° C.

In analogy to this example the compounds listed in tables 1 to 4 areprepared.

                                      TABLE 1                                     __________________________________________________________________________     ##STR29##                                                                    No. AQ                      phys. data                                        __________________________________________________________________________    1.001                                                                             CH.sub.2COOH                                                              1.002                                                                             CH.sub.2COOCH.sub.3     m.p. 98-99°                                1.003                                                                             CH.sub.2COOC.sub.2 H.sub.5                                                                            n.sub.D.sup.23 1,5869                             1.004                                                                             CH.sub.2COOC.sub.3 H.sub.7 -n                                             1.005                                                                             CH.sub.2COOCH(CH.sub.3).sub.2                                                                         n.sub.D.sup.23 1,5799                             1.006                                                                             CH.sub.2COOC.sub.4 H.sub.9 -n                                                                         n.sub.D.sup.23 1,5748                             1.007                                                                             CH.sub.2COOCH.sub.2 CH(CH.sub.3).sub.2                                    1.008                                                                             CH.sub.2COOCH(CH.sub.3)C.sub.2 H.sub.5                                    1.009                                                                             CH.sub.2COOC(CH.sub.3).sub.3                                              1.010                                                                             CH.sub.2COO(CH.sub.2).sub.9 CH.sub.3                                      1.011                                                                             CH.sub.2COOCH.sub.2 CH.sub.2 OCH.sub.3                                                                n.sub.D.sup.23 1,5812                             1.012                                                                              CH.sub.2COOCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                            1.013                                                                             CH.sub.2COOCH.sub.2 CH.sub.2 OC.sub.3 H.sub.7 -n                          1.014                                                                             CH.sub.2COO Cyclohexyl  n.sub.D.sup.23 1,5702                             1.015                                                                             CH.sub.2COOCH.sub.2 CH.sub.2 OCH.sub.2 CHCH.sub.2                         1.016                                                                             CH.sub.2COOC(CH.sub.3).sub.2 CN                                           1.017                                                                             CH.sub.2 COOCH.sub.2 CH.sub.2 SCH.sub.3                                   1.018                                                                             CH.sub.2 COOCH(CH.sub.3)CH.sub.2 N(CH.sub.3).sub.2                        1.019                                                                             CH(CH.sub.3)COOH        m.p. 144-146°                              1.020                                                                             CH(CH.sub.3)COOCH.sub.3 n.sub.D.sup.20 1,5855                             1.021                                                                             CH(CH.sub.3)COOC.sub.2 H.sub.5                                                                        n.sub.D.sup.22 1,5722                             1.022                                                                             CH(CH.sub.3)COOC.sub.3 H.sub.7 -n                                         1.023                                                                             CH(CH.sub.3)COOCH(CH.sub.3).sub.2                                                                     n.sub.D.sup.22 1,5705                             1.024                                                                             CH(CH.sub.3)COOC.sub.4 H.sub.9 -n                                         1.025                                                                             CH(CH.sub.3)COOCH.sub.2 CH(CH.sub.3).sub.2                                1.026                                                                             CH(CH.sub.3)COOCH(CH.sub.3)C.sub.2 H.sub.5                                1.027                                                                             CH(CH.sub.3)COOC(CH.sub.3).sub.3                                                                      n.sub.D.sup.22 1,5418                             1.028                                                                             CH(CH.sub.3)COOC.sub.5 H.sub.11 -n                                        1.029                                                                             CH(CH.sub.3)COOCH.sub.2 CH.sub.2 OCH.sub.3                                1.030                                                                             CH(CH.sub.3)COOCH.sub. 2 CH.sub.2 OC.sub.2 H.sub.5                        1.031                                                                             CH(CH.sub.3)COOCH.sub.2 CH.sub.2 OC.sub.3 H.sub.7 -n                      1.032                                                                             CH(CH.sub.3)COOCH.sub.2 CH.sub.2 OCH.sub.2 CHCH.sub.2                     1.033                                                                             CH(CH.sub.3)COOC(CH.sub.3).sub.2 CN                                       1.034                                                                             CH(CH.sub.3)COOCH.sub.2 CH.sub.2 SCH.sub.3                                1.035                                                                             CH(CH.sub.3)CH.sub.2 OH                                                   1.036                                                                             CH(CH.sub.3)CN                                                            1.037                                                                             C.sub.2 H.sub.4 OH                                                        1.038                                                                             CH(CH.sub.3)CH.sub.2 Cl                                                   1.039                                                                             C.sub.2 H.sub.4 Cl                                                        1.040                                                                             CH.sub.2 CN                                                               1.041                                                                             CH.sub.2 C(CH.sub.3).sub.2 OH                                             1.042                                                                             CH.sub.2 SCN                                                              1.043                                                                             C.sub.2 H.sub.4 CN                                                        1.044                                                                             CH(CH.sub.3)CH.sub.2 CN                                                   1.045                                                                             CH(CH.sub.2 OCH.sub.3)COOCH.sub.3                                         1.046                                                                             CH.sub.2 CH(OCH.sub.3)COOCH.sub.3                                         1.047                                                                             CH(CH.sub.3)COOC.sub.2 H.sub.4 OCH.sub.2 CHCH.sub.2                       1.048                                                                             CH(CN)CH.sub.2 OCH.sub.3                                                  1.049                                                                             CH.sub.2 CH(SCH.sub.3)COOCH.sub.3                                         1.050                                                                             CH.sub.2 CHCH.sub.2                                                       1.051                                                                             CH.sub.2 CHCHCl                                                           1.052                                                                             CH.sub.2 CClCH.sub.2                                                      1.053                                                                             CH.sub.2 CHCHCN                                                           1.054                                                                             CH.sub.2 C CH                                                             1.055                                                                             CH.sub.2 C(CH.sub.3)CHCOOCH.sub.3                                         1.056                                                                             C.sub.2 H.sub.4 N(CH.sub.3).sub.2                                         1.057                                                                             C.sub.2 H.sub.4 -pyrrolidino                                              1.058                                                                             C.sub.2 H.sub.4 -piperidino                                               1.059                                                                             C.sub.2 H.sub.4 -morpholino                                               1.060                                                                             CH[N(CH.sub.3).sub.2 ]COOCH.sub.3                                         1.061                                                                             CH(CH.sub.3)CH.sub.2 N(CH.sub.3).sub.2                                    1.062                                                                             CH(CH.sub.3)CO-piperidino                                                 1.063                                                                             CH(CH.sub.3)CO-pyrrolidino                                                1.064                                                                             CH(CH.sub.3)CO-4-methylpiperazino                                         1.065                                                                             CH(CH.sub.3)CO-morpholino                                                 1.066                                                                             CH(CH.sub.3)CO-2-methylmorpholino                                         1.067                                                                             CH(CH.sub.3)CO-2,6-dimethylmorpholino                                     1.068                                                                             CH(CH.sub.3)CO-2-methylpiperidino                                         1.069                                                                             CH(CH.sub.3)CO-3-methylpiperidino                                         1.070                                                                             CH(CH.sub.3)CO-4-methylpiperidino                                         1.071                                                                             CH(CH.sub.3)CON(CH.sub.3)CH.sub.2 CN                                      1.072                                                                             CH(CH.sub.3)CON(CH.sub.2 CHCH.sub.2).sub.2                                1.073                                                                             CH(CH.sub.3)COOCH.sub.2 Si(CH.sub.3).sub.3                                1.074                                                                             CH(CH.sub.3)COOC.sub.2 H.sub.4 Si(CH.sub.3).sub.3                         1.075                                                                             CH(CH.sub.3)COONC(CH.sub.3).sub.2                                         1.076                                                                             CH(CH.sub.3)COONcyclopentyl                                               1.077                                                                             CH(CH.sub.3)COONcyclohexyl                                                1.078                                                                         1,3-dioxolan-2-yleth-1-yl                                                     1.079                                                                         1,3-dioxolan-2-ylmethyl                                                       1.080                                                                         4-methyl-1,3-dioxolan-2-ylmethyl                                              1.081                                                                         1,3-dioxolan-2-ylpropyl                                                       1.082                                                                         2-methyl-1,3-dioxolan-2-ylpropyl                                              1.083                                                                             C.sub.2 H.sub.4 C(OCH.sub.3).sub.2                                        1.084                                                                             C.sub. 2 H.sub.4 C(OC.sub.2 H.sub.5).sub.2                                1.085                                                                             CH(CH.sub.3)C(OC.sub.2 H.sub.5).sub.2                                     1.086                                                                             CH(CH.sub.3)C(OCH.sub.3).sub.2                                            1.087                                                                         2-methyl-1,3-dioxolan-2-ylmethyl                                              1.088                                                                             C.sub.2 H.sub.4 Si(OC.sub.2 H.sub.5).sub.3                                1.089                                                                             CH.sub.2 Si(CH.sub.3).sub.3                                                                           n.sub.D.sup.23 1,5801                             1.090                                                                             CH(CH.sub.3)Si(CH.sub.3).sub.3                                            1.091                                                                             C.sub.2 H.sub.4 Si(CH.sub.3).sub.3                                        1.092                                                                             CH(CH.sub.3)CH.sub.2 Si(CH.sub.3).sub.3                                   1.093                                                                             CH(CH.sub.3)PO(OC.sub.2 H.sub.5).sub.2                                    1.094                                                                             CH(CH.sub.3)PO(CH.sub.3)OC.sub.2 H.sub.5                                  1.095                                                                             CH(CH.sub.3)CON(CH.sub.3)SO.sub.2 CH.sub.3                                1.096                                                                             CH(CH.sub.3)CON(CH.sub.3)SO.sub.2 CH.sub.2 Cl                             1.097                                                                             CH.sub.2 CON(CH.sub.3)SO.sub.2 CH.sub.3                                   1.098                                                                             CH(CH.sub.3)CON(CH.sub.2 CHCH.sub.2)SO.sub.2 CH.sub.3                     1.099                                                                             CH(CH.sub.3)CON(cyclopropyl)SO.sub.2 CH.sub.3                             1.100                                                                             CH(CH.sub.3)CON[CH(CH.sub.3).sub.2 ]SO.sub.2 CH.sub.3                     1.101                                                                             CH.sub.2 COCH.sub.3                                                       1.102                                                                             CH.sub.2 CO benzyl                                                        1.103                                                                             CH.sub.2 CO phenyl                                                        1.104                                                                             CH.sub.2 COCH.sub.2 OCH.sub.3                                             1.105                                                                             CH(CH.sub.3)COCH.sub.3                                                    1.106                                                                             CH(CH.sub.3)COCH.sub.2 COOCH.sub.3                                        1.107                                                                             CH(COCH.sub.3)COOC.sub.2 H.sub.5                                          1.108                                                                             CH(CH.sub.3)COOCH(CH.sub.3)CH.sub.2 SCH.sub.3                             1.109                                                                             CH(CH.sub.3)COOCH(CH.sub.3)CH.sub.2 SC.sub.2 H.sub.5                      1.110                                                                             CH(CH.sub.3)COOCH(CH.sub.3)CH.sub.2 SC.sub.3 H.sub.7 -n                   1.111                                                                             CH(CH.sub.3)COOCH(CH.sub.3)CH.sub.2 SCH(CH.sub.3).sub.2                   1.112                                                                             CH(CH.sub.3)COOCH(CH.sub.3)CH.sub.2 SC.sub.4 H.sub.9 -n                   1.113                                                                             CH(CH.sub.3)COOCH(CH.sub.3)CH.sub.2 SC(CH.sub.3).sub.3                    1.114                                                                             CH(CH.sub.3)COOCH(CH.sub.3)CH.sub.2 SCH(CH.sub.3)C.sub.2 H.sub.5          1.115                                                                             CH(CH.sub.3)CON(CH.sub.3)CH.sub.2 CH(OCH.sub.3).sub.2                     1.116                                                                             CH(CH.sub.3)CON(CH.sub.3)CH.sub.2 CH(OC.sub.2 H.sub.5).sub.2              1.117                                                                             CH(CH.sub.3)COOC.sub.2 H.sub.4 OCH.sub.2 CHCH.sub.2                       1.118                                                                             CH(COCH.sub.3).sub.2                                                      1.119                                                                             CH(CN)COOCH.sub.3                                                         1.120                                                                             CH(OCH.sub.3)COOCH.sub.3                                                  1.121                                                                              ##STR30##              n.sub.D.sup.25 1,5828                             1.122                                                                             C.sub.2 H.sub.4 COOCH.sub.3                                                                           n.sub.D.sup.25 1,5655                             1.123                                                                             C.sub.2 H.sub.4 COOC.sub.2 H.sub.5                                                                    n.sub.D.sup.25 1,5615                             __________________________________________________________________________

                  TABLE 2                                                         ______________________________________                                         ##STR31##                                                                                                      phys.                                       No.   AQ                          data                                        ______________________________________                                        2.001 CH.sub.2COOH                                                            2.002 CH.sub.2COOCH.sub.3                                                     2.003 CH.sub.2COOC.sub.2 H.sub.5                                              2.004 CH.sub.2COOC.sub.3 H.sub.7 -n                                           2.005 CH.sub.2COOCH(CH.sub.3).sub.2                                           2.006 CH.sub.2COOC.sub.4 H.sub.9 -n                                           2.007 CH.sub.2COOCH.sub.2 CH(CH.sub.3).sub.2                                  2.008 CH.sub.2COOCH(CH.sub.3)C.sub.2 H.sub.5                                  2.009 CH.sub.2COOC(CH.sub.3).sub.3                                            2.010 CH.sub.2COO(CH.sub.2).sub.9 CH.sub.3                                    2.011 CH.sub.2COOCH.sub.2 CH.sub.2 OCH.sub.3                                  2.012 CH.sub.2COOCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                           2.013 CH.sub.2COOCH.sub.2 CH.sub.2 OC.sub.3 H.sub.7 -n                        2.014 CH.sub.2COO Cyclohexyl                                                  2.015 CH.sub.2COOCH.sub.2 CH.sub.2 OCH.sub.2 CHCH.sub.2                       2.016 CH.sub.2COOC(CH.sub.3).sub.2 CN                                         2.017 CH.sub.2 COOCH.sub.2 CH.sub.2 SCH.sub.3                                 2.018 CH.sub.2COOCH(CH.sub.3)CH.sub.2 N(CH.sub.3).sub.2                       2.019 CH(CH.sub.3)COOH                                                        2.020 CH(CH.sub.3)COOCH.sub.3                                                 2.021 CH(CH.sub.3)COOC.sub.2 H.sub.5                                          2.022 CH(CH.sub.3)COOC.sub.3 H.sub.7 -n                                       2.023 CH(CH.sub.3)COOCH(CH.sub.3).sub.2                                       2.024 CH(CH.sub.3)COOC.sub.4 H.sub.9 -n                                       2.025 CH(CH.sub.3)COOCH.sub.2 CH(CH.sub.3).sub.2                              2.026 CH(CH.sub.3)COOCH(CH.sub.3)C.sub.2 H.sub.5                              2.027 CH(CH.sub.3)COOC(CH.sub.3).sub.3                                        2.028 CH(CH.sub.3)COOC.sub.5 H.sub.11 -n                                      2.029 CH(CH.sub.3)COOCH.sub.2 CH.sub.2 OCH.sub.3                              2.030 CH(CH.sub.3)COOCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                       2.031 CH(CH.sub.3)COOCH.sub.2 CH.sub.2 OC.sub.3 H.sub.7 -n                    2.032 CH(CH.sub.3)COOCH.sub.2 CH.sub.2 OCH.sub.2 CHCH.sub.2                   2.033 CH(CH.sub.3)COOC(CH.sub.3).sub.2 CN                                     2.034 CH(CH.sub.3)COOCH.sub.2 CH.sub.2 SCH.sub.3                              2.035 CH(CH.sub.3)CH.sub.2 OH                                                 2.036 CH(CH.sub.3)CN                                                          2.037 C.sub.2 H.sub.4 OH                                                      2.038 CH(CH.sub.3)CH.sub.2 Cl                                                 2.039 C.sub.2 H.sub.4 Cl                                                      2.040 CH.sub.2 CN                                                             2.041 CH.sub.2 C(CH.sub.3).sub.2 OH                                           2.042 CH.sub.2 SCN                                                            2.043 C.sub.2 H.sub.4 CN                                                      2.044 CH(CH.sub.3)CH.sub.2 CN                                                 2.045 CH(CH.sub.2 OCH.sub.3)COOCH.sub.3                                       2.046 CH.sub.2 CH(OCH.sub.3)COOCH.sub.3                                       2.047 CH(CH.sub.3)COOC.sub.2 H.sub.4 OCH.sub.2 CHCH.sub.2                     2.048 CH(CN)CH.sub.2 OCH.sub.3                                                2.049 CH.sub.2 CH(SCH.sub.3)COOCH.sub.3                                       2.050 CH.sub.2 CHCH.sub.2                                                     2.051 CH.sub.2 CHCHCl                                                         2.052 CH.sub.2 CClCH.sub.2                                                    2.053 CH.sub.2 CHCHCN                                                         2.054 CH.sub.2 CCH                                                            2.055 CH.sub.2 C(CH.sub.3)CHCOOCH.sub.3                                       2.056 C.sub.2 H.sub.4 N(CH.sub.3).sub.2                                       2.057 C.sub.2 H.sub.4 -pyrrolidino                                            2.058 C.sub.2 H.sub.4 -piperidino                                             2.059 C.sub.2 H.sub.4 -morpholino                                             2.060 CH[N(CH.sub.3).sub.2 ]COOCH.sub.3                                       2.061 CH(CH.sub.3)CH.sub.2 N(CH.sub.3).sub.2                                  2.062 CH(CH.sub.3)CO-piperidino                                               2.063 CH(CH.sub.3)CO-pyrrolidino                                              2.064 CH(CH.sub.3)CO-4-methylpiperazino                                       2.065 CH(CH.sub.3)CO-morpholino                                               2.066 CH(CH.sub.3)CO-2-methylmorpholino                                       2.067 CH(CH.sub.3)CO-2,6-dimethylmorpholino                                   2.068 CH(CH.sub.3)CO-2-methylpiperidino                                       2.069 CH(CH.sub.3)CO-3-methylpiperidino                                       2.070 CH(CH.sub.3)CO-4-methylpiperidino                                       2.071 CH(CH.sub.3)CON(CH.sub.3)CH.sub.2 CN                                    2.072 CH(CH.sub.3)CON(CH.sub.2 CHCH.sub.2).sub.2                              2.073 CH(CH.sub.3)COOCH.sub.2 Si(CH.sub.3).sub.3                              2.074 CH(CH.sub.3)COOC.sub.2 H.sub.4 Si(CH.sub.3).sub.3                       2.075 CH(CH.sub.3)COONC(CH.sub.3).sub.2                                       2.076 CH(CH.sub.3)COONcyclopentyl                                             2.077 CH(CH.sub.3)COONcyclohexyl                                              2.078                                                                         1,3-dioxolan-2-yleth-1-yl                                                     2.079                                                                         1,3-dioxolan-2-ylmethyl                                                       2.080                                                                         4-methyl-1,3-dioxolan-2-ylmethyl                                              2.081                                                                         1,3-dioxolan-2-ylpropyl                                                       2.082                                                                         2-methyl-1,3-dioxolan-2-ylpropyl                                              2.083 C.sub.2 H.sub.4 C(OCH.sub.3).sub.2                                      2.084 C.sub.2 H.sub.4 C(OC.sub.2 H.sub.5).sub.2                               2.085 CH(CH.sub.3)C(OC.sub.2 H.sub.5).sub.2                                   2.086 CH(CH.sub.3)C(OCH.sub.3).sub.2                                          2.087                                                                         2-methyl-1,3-dioxolan-2-ylmethyl                                              2.088 C.sub.2 H.sub.4 Si(OC.sub.2 H.sub.5).sub.3                              2.089 CH.sub.2 Si(CH.sub.3).sub.3                                             2.090 CH(CH.sub.3 )Si(CH.sub.3).sub.3                                         2.091 C.sub.2 H.sub.4 Si(CH.sub.3).sub.3                                      2.092 CH(CH.sub.3)CH.sub.2 Si(CH.sub.3).sub.3                                 2.093 CH(CH.sub.3)PO(OC.sub.2 H.sub.5).sub.2                                  2.094 CH(CH.sub.3)PO(CH.sub.3)OC.sub.2 H.sub.5                                2.095 CH(CH.sub.3)CON(CH.sub.3)SO.sub.2 CH.sub.3                              2.096 CH(CH.sub.3)CON(CH.sub.3)SO.sub.2 CH.sub.2 Cl                           2.097 CH.sub.2 CON(CH.sub.3)SO.sub.2 CH.sub.3                                 2.098 CH(CH.sub.3)CON(CH.sub.2 CHCH.sub.2)SO.sub.2 CH.sub.3                   2.099 CH(CH.sub.3)CON(cyclopropyl)SO.sub.2 CH.sub.3                           2.100 CH(CH.sub.3)CON[CH(CH.sub.3).sub.2 ]SO.sub.2 CH.sub.3                   2.101 CH.sub.2 COCH.sub.3                                                     2.102 CH.sub.2 CO benzyl                                                      2.103 CH.sub.2 CO phenyl                                                      2.104 CH.sub.2 COCH.sub.2 OCH.sub.3                                           2.105 CH(CH.sub.3)COCH.sub.3                                                  2.106 CH(CH.sub.3)COCH.sub.2 COOCH.sub.3                                      2.107 CH(COCH.sub.3)COOC.sub.2 H.sub.5                                        2.108 CH(CH.sub.3)COOCH(CH.sub.3)CH.sub.2 SCH.sub.3                           2.109 CH(CH.sub.3)COOCH(CH.sub.3)CH.sub.2 SC.sub.2 H.sub.5                    2.110 CH(CH.sub.3)COOCH(CH.sub.3)CH.sub.2 SC.sub.3 H.sub.7 -n                 2.111 CH(CH.sub.3)COOCH(CH.sub.3)CH.sub. 2 SCH(CH.sub.3).sub.2                2.112 CH(CH.sub.3)COOCH(CH.sub.3)CH.sub.2 SC.sub.4 H.sub.9 -n                 2.113 CH(CH.sub.3)COOCH(CH.sub.3)CH.sub.2 SC(CH.sub.3).sub.3                  2.114 CH(CH.sub.3)COOCH(CH.sub.3)CH.sub.2 SCH(CH.sub.3)C.sub.2 H.sub.5        2.115 CH(CH.sub.3)CON(CH.sub.3)CH.sub.2 CH(OCH.sub.3).sub.2                   2.116 CH(CH.sub.3)CON(CH.sub.3)CH.sub.2 CH(OC.sub.2 H.sub.5).sub.2            2.117 CH(CH.sub.3)COOC.sub.2 H.sub.4 OCH.sub.2 CHCH.sub.2                     2.118 CH(COCH.sub.3).sub.2                                                    2.119 CH(CN)COOCH.sub.3                                                       2.120 CH(OCH.sub.3)COOCH.sub.3                                                2.121 CH.sub.2 CH.sub.2 COOC.sub.2 H.sub.5                                    2.122 CH.sub.2 CH.sub.2 COOCH.sub.3                                           ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                         ##STR32##                                                                                                      phys.                                       No.   AQ                          data                                        ______________________________________                                        3.001 CH.sub.2COOH                                                            3.002 CH.sub.2COOCH.sub.3                                                     3.003 CH.sub.2COOC.sub.2 H.sub.5                                              3.004 CH.sub.2COOC.sub.3 H.sub.7 -n                                           3.005 CH.sub.2COOCH(CH.sub.3).sub.2                                           3.006 CH.sub.2COOC.sub.4 H.sub.9 -n                                           3.007 CH.sub.2COOCH.sub.2 CH(CH.sub.3).sub.2                                  3.008 CH.sub.2COOCH(CH.sub.3)C.sub.2 H.sub.5                                  3.009 CH.sub.2COOC(CH.sub.3).sub.3                                            3.010 CH.sub.2COO(CH.sub.2).sub.9 CH.sub.3                                    3.011 CH.sub.2COOCH.sub.2 CH.sub.2 OCH.sub.3                                  3.012 CH.sub.2COOCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                           3.013 CH.sub.2COOCH.sub.2 CH.sub.2 OC.sub.3 H.sub.7 -n                        3.014 CH.sub.2 COO Cyclohexyl                                                 3.015 CH.sub.2COOCH.sub.2 CH.sub.2 OCH.sub.2 CHCH.sub.2                       3.016 CH.sub.2COOC(CH.sub.3).sub.2 CN                                         3.017 CH.sub.2 COOCH.sub.2 CH.sub.2 SCH.sub.3                                 3.018 CH.sub.2COOCH(CH.sub.3)CH.sub.2 N(CH.sub.3).sub.2                       3.019 CH(CH.sub.3)COOH                                                        3.020 CH(CH.sub.3)COOCH.sub.3                                                 3.021 CH(CH.sub.3)COOC.sub.2 H.sub.5                                          3.022 CH(CH.sub.3)COOC.sub.3 H.sub.7 -n                                       3.023 CH(CH.sub.3)COOCH(CH.sub.3).sub.2                                       3.024 CH(CH.sub.3)COOC.sub.4 H.sub.9 -n                                       3.025 CH(CH.sub.3)COOCH.sub.2 CH(CH.sub.3).sub.2                              3.026 CH(CH.sub.3)COOCH(CH.sub.3)C.sub.2 H.sub.5                              3.027 CH(CH.sub.3)COOC(CH.sub.3).sub.3                                        3.028 CH(CH.sub.3)COOC.sub.5 H.sub.11 -n                                      3.029 CH(CH.sub.3)COOCH.sub.2 CH.sub.2 OCH.sub.3                              3.030 CH(CH.sub.3)COOCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                       3.031 CH(CH.sub.3)COOCH.sub.2 CH.sub.2 OC.sub.3 H.sub.7 -n                    3.032 CH(CH.sub.3)COOCH.sub.2 CH.sub.2 OCH.sub.2 CHCH.sub.2                   3.033 CH(CH.sub.3)COOC(CH.sub.3).sub.2 CN                                     3.034 CH(CH.sub.3)COOCH.sub.2 CH.sub.2 SCH.sub.3                              3.035 CH(CH.sub.3 )CH.sub.2 OH                                                3.036 CH(CH.sub.3)CN                                                          3.037 C.sub.2 H.sub.4 OH                                                      3.038 CH(CH.sub.3)CH.sub.2 Cl                                                 3.039 C.sub.2 H.sub.4 Cl                                                      3.040 CH.sub.2 CN                                                             3.041 CH.sub.2 C(CH.sub.3).sub.2 OH                                           3.042 CH.sub.2 SCN                                                            3.043 C.sub.2 H.sub.4 CN                                                      3.044 CH(CH.sub.3)CH.sub.2 CN                                                 3.045 CH(CH.sub.2 OCH.sub.3)COOCH.sub.3                                       3.046 CH.sub.2 CH(OCH.sub.3)COOCH.sub.3                                       3.047 CH(CH.sub.3)COOC.sub.2 H.sub.4 OCH.sub.2 CHCH.sub.2                     3.048 CH(CN)CH.sub.2 OCH.sub.3                                                3.049 CH.sub.2 CH(SCH.sub.3)COOCH.sub.3                                       3.050 CH.sub.2 CHCH.sub.2                                                     3.051 CH.sub.2 CHCHCl                                                         3.052 CH.sub.2 CClCH.sub.2                                                    3.053 CH.sub.2 CHCHCN                                                         3.054 CH.sub.2 CCH                                                            3.055 CH.sub.2 C(CH.sub.3)CHCOOCH.sub.3                                       3.056 C.sub.2 H.sub.4 N(CH.sub.3).sub.2                                       3.057 C.sub.2 H.sub.4 -pyrrolidino                                            3.058 C.sub.2 H.sub.4 -piperidino                                             3.059 C.sub.2 H.sub.4 -morpholino                                             3.060 CH[N(CH.sub.3).sub.2 ]COOCH.sub.3                                       3.061 CH(CH.sub.3 )CH.sub.2 N(CH.sub.3).sub.2                                 3.062 CH(CH.sub.3)CO-piperidino                                               3.063 CH(CH.sub.3)CO-pyrrolidino                                              3.064 CH(CH.sub.3)CO-methylpiperazino                                         3.065 CH(CH.sub.3)CO-morpholino                                               3.066 CH(CH.sub.3)CO-2-methylmorpholino                                       3.067 CH(CH.sub.3)CO-2,6-dimethylmorpholino                                   3.068 CH(CH.sub.3)CO-2-methylpiperidino                                       3.069 CH(CH.sub.3)CO-3-methylpiperidino                                       3.070 CH(CH.sub.3)CO-4-methylpiperidino                                       3.071 CH(CH.sub.3)CON(CH.sub.3)CH.sub.2 CN                                    3.072 CH(CH.sub.3)CON(CH.sub.2 CHCH.sub.2).sub.2                              3.073 CH(CH.sub.3)COOCH.sub.2 Si(CH.sub.3).sub.3                              3.074 CH(CH.sub.3)COOC.sub.2 H.sub.4 Si(CH.sub.3).sub.3                       3.075 CH(CH.sub.3)COONC(CH.sub.3).sub.2                                       3.076 CH(CH.sub.3)COONcyclopentyl                                             3.077 CH(CH.sub.3)COONcyclohexyl                                              3.078                                                                         1,3-dioxolan-2-yleth-1-yl                                                     3.079                                                                         1,3-dioxolan-2-ylmethyl                                                       3.080                                                                         4-methyl-1,3-dioxolan-2-ylmethyl                                              3.081                                                                         1,3-dioxolan-2-ylpropyl                                                       3.082                                                                         2-methyl-1,3-dioxolan-2-ylpropyl                                              3.083 C.sub.2 H.sub.4 C(OCH.sub.3).sub.2                                      3.084 C.sub.2 H.sub.4 C(OC.sub.2 H.sub.5).sub.2                               3.085 CH(CH.sub.3)C(OC.sub.2 H.sub.5).sub.2                                   3.086 CH(CH.sub.3)C(OCH.sub.3).sub.2                                          3.087                                                                         2-methyl-1,3-dioxolan-2-ylmethyl                                              3.088 C.sub.2 H.sub.4 Si(OC.sub.2 H.sub.5).sub.3                              3.089 CH.sub.2 Si(CH.sub.3).sub.3                                             3.090 CH(CH.sub.3)Si(CH.sub.3).sub. 3                                         3.091 C.sub.2 H.sub.4 Si(CH.sub.3).sub.3                                      3.092 CH(CH.sub.3)CH.sub.2 Si(CH.sub.3).sub.3                                 3.093 CH(CH.sub.3)PO(OC.sub.2 H.sub.5).sub.2                                  3.094 CH(CH.sub.3)PO(CH.sub.3)OC.sub.2 H.sub.5                                3.095 CH(CH.sub.3)CON(CH.sub.3)SO.sub.2 CH.sub.3                              3.096 CH(CH.sub.3)CON(CH.sub.3)SO.sub.2 CH.sub.2 Cl                           3.097 CH.sub.2 CON(CH.sub.3)SO.sub.2 CH.sub.3                                 3.098 CH(CH.sub.3)CON(CH.sub.2 CHCH.sub.2)SO.sub.2 CH.sub.3                   3.099 CH(CH.sub.3)CON(cyclopropyl)SO.sub.2 CH.sub.3                           3.100 CH(CH.sub.3)CON[CH(CH.sub.3).sub.2 ]SO.sub.2 CH.sub.3                   3.101 CH.sub.2 COCH.sub.3                                                     3.102 CH.sub.2 CO benzyl                                                      3.103 CH.sub.2 CO phenyl                                                      3.104 CH.sub.2 COCH.sub.2 OCH.sub.3                                           3.105 CH(CH.sub.3)COCH.sub.3                                                  3.106 CH(CH.sub.3)COCH.sub.2 COOCH.sub.3                                      3.107 CH(COCH.sub.3)COOC.sub.2 H.sub.5                                        3.108 CH(CH.sub.3)COOCH(CH.sub.3)CH.sub.2 SCH.sub.3                           3.109 CH(CH.sub.3)COOCH(CH.sub.3)CH.sub.2 SC.sub.2 H.sub.5                    3.110 CH(CH.sub.3)COOCH(CH.sub.3)CH.sub.2 SC.sub.3 H.sub.7 -n                       -3.111 CH(CH.sub.3)COOCH(CH.sub.3)CH.sub.2 SCH(CH.sub.3 ).sub.2         3.112 CH(CH.sub.3)COOCH(CH.sub.3)CH.sub.2 SC.sub.4 H.sub.9 -n                 3.113 CH(CH.sub.3)COOCH(CH.sub.3)CH.sub.2 SC(CH.sub.3).sub.3                  3.114 CH(CH.sub.3)COOCH(CH.sub.3)CH.sub.2 SCH(CH.sub.3)C.sub.2 H.sub.5        3.115 CH(CH.sub.3)CON(CH.sub.3)CH.sub.2 CH(OCH.sub.3).sub.2                   3.116 CH(CH.sub.3)CON(CH.sub.3)CH.sub.2 CH(OC.sub.2 H.sub.5).sub.2            3.117 CH(CH.sub.3)COOC.sub.2 H.sub.4 OCH.sub.2 CHCH.sub.2                     3.118 CH(COCH.sub.3).sub.2                                                    3.119 CH(CN)COOCH.sub.3                                                       3.120 CH(OCH.sub.3)COOCH.sub.3                                                ______________________________________                                    

                                      TABLE 4                                     __________________________________________________________________________     ##STR33##                                                                    No.  AQ                       phys. data                                      __________________________________________________________________________    4.001                                                                              CH.sub.2COOH                                                             4.002                                                                              CH.sub.2COOCH.sub.3      n.sub.D.sup.24 1,5832                           4.003                                                                              CH.sub.2COOC.sub.2 H.sub.5                                                                             n.sub.D.sup.25 1,5795                           4.004                                                                              CH.sub.2COOC.sub.3 H.sub.7 -n                                            4.005                                                                              CH.sub.2COOCH(CH.sub.3).sub.2                                            4.006                                                                              CH.sub.2COOC.sub.4 H.sub.9 -n                                            4.007                                                                              CH.sub.2COOCH.sub.2 CH(CH.sub.3).sub.2                                   4.008                                                                              CH.sub.2COOCH(CH.sub.3)C.sub.2 H.sub.5                                   4.009                                                                              CH.sub.2COOC(CH.sub.3).sub.3                                             4.010                                                                              CH.sub.2COO(CH.sub.2).sub.9 CH.sub.3                                     4.011                                                                              CH.sub.2COOCH.sub.2 CH.sub.2 OCH.sub.3                                                                 n.sub.D.sup.25 1,5578                           4.012                                                                              CH.sub.2COOCH.sub.2 CH.sub.2 OC.sub. 2 H.sub.5                           4.013                                                                              CH.sub.2COOCH.sub.2 CH.sub.2 OC.sub.3 H.sub.7 -n                         4.014                                                                              CH.sub.2COO Cyclohexyl                                                   4.015                                                                              CH.sub.2COOCH.sub.2 CH.sub.2 OCH.sub.2 CHCH.sub.2                        4.016                                                                              CH.sub.2COOC(CH.sub.3).sub.2 CN                                          4.017                                                                              CH.sub.2 COOCH.sub.2 CH.sub.2 SCH.sub.3                                  4.018                                                                              CH.sub.2COOCH(CH.sub.3)CH.sub.2 N(CH.sub.3).sub.2                        4.019                                                                              CH(CH.sub.3)COOH                                                         4.020                                                                              CH(CH.sub.3)COOCH.sub.3  n.sub.D.sup.24 1,5749                           4.021                                                                              CH(CH.sub.3)COOC.sub.2 H.sub.5                                                                         n.sub.D.sup.26 1,5428                           4.022                                                                              CH(CH.sub.3)COOC.sub.3 H.sub.7 -n                                                                      n.sub.D.sup.21 1,5491                           4.023                                                                              CH(CH.sub.3)COOCH(CH.sub.3).sub.2                                                                      n.sub.D.sup.26 1,5394                           4.024                                                                              CH(CH.sub.3)COOC.sub.4 H.sub.9 -n                                        4.025                                                                              CH(CH.sub.3)COOCH.sub.2 CH(CH.sub.3).sub.2                               4.026                                                                              CH(CH.sub.3)COOCH(CH.sub.3)C.sub.2 H.sub.5                               4.027                                                                              CH(CH.sub.3)COOC(CH.sub.3).sub.3                                         4.028                                                                              CH(CH.sub.3)COOC.sub.5 H.sub.11 -n                                       4.029                                                                              CH(CH.sub.3)COOCH.sub.2 CH.sub.2 OCH.sub.3                               4.030                                                                              CH(CH.sub.3)COOCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                        4.031                                                                              CH(CH.sub.3)COOCH.sub.2 CH.sub.2 OC.sub. 3 H.sub.7 -n                    4.032                                                                              CH(CH.sub.3)COOCH.sub.2 CH.sub.2 OCH.sub.2 CHCH.sub.2                    4.033                                                                              CH(CH.sub.3)COOC(CH.sub.3).sub.2 CN                                      4.034                                                                              CH(CH.sub.3)COOCH.sub.2 CH.sub.2 SCH.sub.3                               4.035                                                                              CH(CH.sub.3)CH.sub.2 OH                                                  4.036                                                                              CH(CH.sub.3)CN                                                           4.037                                                                              C.sub.2 H.sub.4 OH                                                       4.038                                                                              CH(CH.sub.3)CH.sub.2 Cl                                                  4.039                                                                              C.sub.2 H.sub.4 Cl                                                       4.040                                                                              CH.sub.2 CN                                                              4.041                                                                              CH.sub.2 C(CH.sub.3).sub.2 OH                                            4.042                                                                              CH.sub.2 SCN                                                             4.043                                                                              C.sub.2 C.sub.4 CN                                                       4.044                                                                              CH(CH.sub.3)CH.sub.2 CN                                                  4.045                                                                              CH(CH.sub.2 OCH.sub.3)COOCH.sub.3                                        4.046                                                                              CH.sub.2 CH(OCH.sub.3)COOCH.sub.3                                        4.047                                                                              CH(CH.sub.3)COOC.sub.2 H.sub.4 OCH.sub.2 CHCH.sub.2                      4.048                                                                              CH(CN)CH.sub.2 OCH.sub.3                                                 4.049                                                                              CH.sub.2 CH(SCH.sub.3)COOCH.sub.3                                        4.050                                                                              CH.sub.2 CHCH.sub.2                                                      4.051                                                                              CH.sub.2 CHCHCl                                                          4.052                                                                              CH.sub.2 CClCH.sub.2                                                     4.053                                                                              CH.sub.2 CHCHCN                                                          4.054                                                                              CH.sub.2 CCH                                                             4.055                                                                              CH.sub.2 C(CH.sub.3)CHCOOCH.sub.3                                        4.056                                                                              C.sub.2 H.sub. 4 N(CH.sub.3).sub.2                                       4.057                                                                              C.sub.2 H.sub.4 -pyrolidino                                              4.058                                                                              C.sub.2 H.sub.4 -piperidino                                              4.059                                                                              C.sub.2 H.sub.4 -morpholino                                              4.060                                                                              CH[N(CH.sub.3).sub.2 ]COOCH.sub.3                                        4.061                                                                              CH(CH.sub.3)CH.sub.2 N(CH.sub.3).sub.2                                   4.062                                                                              CH(CH.sub.3)CO-piperidino                                                4.063                                                                              CH(CH.sub.3)CO-pyrrolidino                                               4.064                                                                              CH(CH.sub.3)CO-4-methylpiperazino                                        4.065                                                                              CH(CH.sub.3)CO-morpholino                                                4.066                                                                              CH(CH.sub.3)CO-2-methymorpholino                                         4.067                                                                              CH(CH.sub.3)CO-2,6-dimethylmorpholino                                    4.068                                                                              CH(CH.sub.3)CO-2-methylpiperidino                                        4.069                                                                              CH(CH.sub.3)CO-3-methylpiperidino                                        4.070                                                                              CH(CH.sub.3)CO-4-methylpiperidino                                        4.071                                                                              CH(CH.sub.3)CON(CH.sub.3)CH.sub.2 CN                                     4.072                                                                              CH(CH.sub.3)CON(CH.sub.2 CHCH.sub.2).sub.2                               4.073                                                                              CH(CH.sub.3)COOCH.sub.2 Si(CH.sub.3).sub.3                               4.074                                                                              CH(CH.sub.3)COOC.sub.2 H.sub.4 Si(CH.sub.3).sub.3                        4.075                                                                              CH(CH.sub.3)COONC(CH.sub.3).sub.2                                        4.076                                                                              CH(CH.sub.3)COONcyclopentyl                                              4.077                                                                              CH(CH.sub.3)COONcyclohexyl                                               4.078                                                                         1,3-dioxolan-2-yleth-1-yl                                                     4.079                                                                         1,3-dioxolan-2-ylmethyl                                                       4.080                                                                         4-methyl-1,3-dioxolan-2-ylmethyl                                              4.081                                                                         1,3-dioxolan-2-ylpropyl                                                       4.082                                                                         2-methyl-1,3-dioxolan-2-ylpropyl                                              4.083                                                                              C.sub.2 H.sub.4 C(OCH.sub.3).sub.2                                       4.084                                                                              C.sub.2 H.sub.4 C(OC.sub.2 H.sub.5).sub.2                                4.085                                                                              CH(CH.sub.3)C(OC.sub.2 H.sub. 5).sub.2                                   4.086                                                                              CH(CH.sub.3)C(OCH.sub.3).sub.2                                           4.087                                                                         2-methyl-1,3-dioxolan-2-ylmethyl                                              4.088                                                                              C.sub.2 H.sub.4 Si(OC.sub.2 H.sub.5).sub.3                               4.089                                                                              CH.sub.2 Si(CH.sub.3).sub.3                                              4.090                                                                              CH(CH.sub.3)Si(CH.sub.3).sub.3                                           4.091                                                                              C.sub.2 H.sub.4 Si(CH.sub.3).sub.3                                       4.092                                                                              CH(CH.sub.3)CH.sub.2 Si(CH.sub.3).sub.3                                  4.093                                                                              CH(CH.sub.3)PO(OC.sub.2 H.sub.5).sub.2                                   4.094                                                                              CH(CH.sub.3)PO(CH.sub.3)OC.sub.2 H.sub.5                                 4.095                                                                              CH(CH.sub.3)CON(CH.sub.3)SO.sub.2 CH.sub.3                               4.096                                                                              CH(CH.sub.3)CON(CH.sub.3)SO.sub.2 CH.sub.2 Cl                            4.097                                                                              CH.sub.2 CON(CH.sub.3)SO.sub.2 CH.sub.3                                  4.098                                                                              CH(CH.sub.3)CON(CH.sub.2 CHCH.sub.2)SO.sub.2 CH.sub.3                    4.099                                                                              CH(CH.sub.3)CON(cyclopropyl)SO.sub.2 CH.sub.3                            4.100                                                                              CH(CH.sub.3)CON[CH(CH.sub.).sub.2 ]SO.sub.2 CH.sub.3                     4.101                                                                              CH.sub.2 COCH.sub.3                                                      4.102                                                                              CH.sub.2 CO benzyl                                                       4.103                                                                              CH.sub.2 CO phenyl                                                       4.104                                                                              CH.sub.2 COCH.sub.2 OCH.sub.3                                            4.105                                                                              CH(CH.sub.3)COCH.sub.3                                                   4.106                                                                              CH(CH.sub.3)COCH.sub.2 COOCH.sub.3                                       4.107                                                                              CH(COCH.sub.3)COOC.sub.2 H.sub.5                                         4.108                                                                              CH(CH.sub.3)COOCH(CH.sub. 3)CH.sub.2 SCH.sub.3                           4.109                                                                              CH(CH.sub.3)COOCH(CH.sub.3)CH.sub.2 SC.sub.2 H.sub.5                     4.110                                                                              CH(CH.sub.3)COOCH(CH.sub.3)CH.sub.2 SC.sub.3 H.sub.7 -n                  4.111                                                                              CH(CH.sub.3)COOCH(CH.sub.3)CH.sub.2 SCH(CH.sub.3).sub.2                  4.112                                                                              CH(CH.sub.3)COOCH(CH.sub.3)CH.sub.2 SC.sub.4 H.sub.9 -n                  4.113                                                                              CH(CH.sub.3)COOCH(CH.sub.3)CH.sub.2 SC(CH.sub.3).sub.3                   4.114                                                                              CH(CH.sub.3)COOCH(CH.sub.3)CH.sub.2 SCH(CH.sub.3)C.sub.2 H.sub.5         4.115                                                                              CH(CH.sub.3)CON(CH.sub.3)CH.sub.2 CH(OCH.sub.3).sub.2                    4.116                                                                              CH(CH.sub.3)CON(CH.sub.3)CH.sub.2 CH(OC.sub.2 H.sub.5).sub.2             4.117                                                                              CH(CH.sub.3)COOC.sub.2 H.sub.4 OCH.sub.2 CHCH.sub.2                      4.118                                                                              CH(COCH.sub.3).sub.2                                                     4.119                                                                              CH(CN)COOCH.sub.3                                                        4.120                                                                              CH(OCH.sub.3)COOCH.sub.3                                                 __________________________________________________________________________

FORMULATION EXAMPLES EXAMPLE 2 Formulation Examples for compounds offormula I (percentages are by weight)

    ______________________________________                                        (a) Wettable powders (a)     (b)     (c)                                      ______________________________________                                        compound of Tables 1 to 4                                                                          20%     60%       0.5%                                   sodium lignosulfonate                                                                              5%      5%      5%                                       sodium laurylsulfate 3%      --      --                                       sodium diisobutylnaphthalenesulfonate                                                              --      6%      6%                                       octylphenol polyethylene glycol ether                                                              --      2%      2%                                       (7-8 moles of ethylene oxide)                                                 highly dispersed silicic acid                                                                      5%      27%     27%                                      kaolin               67%     --      --                                       sodium chloride      --      --       59.5%                                   ______________________________________                                    

The active ingredient is thoroughly mixed with the adjuvants and themixture is thoroughly ground in a suitable mill, affording wettablepowders which can be diluted with water to give suspensions of thedesired concentration.

    ______________________________________                                        (b) Emulsifiable concentrates                                                                         (a)     (b)                                           ______________________________________                                        compound of Tables 1 to 4                                                                             10%     1%                                            octylphenol polyethylene glycol ether                                                                  3%     3%                                            (4-5 moles of ethylene oxide)                                                 calcium dodecylbenzenesulfonate                                                                        3%     3%                                            castor oil polyglycol ether                                                                            4%     4%                                            (36 moles of ethylene oxide)                                                  cyclohexanone           30%     10%                                           xylene mixture          50%     79%                                           ______________________________________                                    

Emulsions of any required concentration can be obtained from thisconcentrate by dilution with water.

    ______________________________________                                        (c) Dusts            (a)     (b)                                              ______________________________________                                        compound of Tables 1 to 4                                                                           0.1%    1%                                              talcum               99.9%   --                                               kaolin               --      99%                                              ______________________________________                                    

Dusts which are ready for use are obtained by mixing the activeingredient with the carrier, and grinding the mixture in a suitablemill.

    ______________________________________                                        (d) Extruder granulates                                                                            (a)     (b)                                              ______________________________________                                        compound of Tables 1 to 4                                                                          10%     1%                                               sodium lignosulfonate                                                                               2%     2%                                               carboxymethylcellulose                                                                              1%     1%                                               kaolin               87%     96%                                              ______________________________________                                    

The active ingredient is mixed and ground with the adjuvants, and themixture is subsequently moistened with water. The mixture is extrudedand then dried in a stream of air.

    ______________________________________                                        (e) Coated granulate                                                          ______________________________________                                        compound of Tables 1 to 4                                                                           3%                                                      polyethylene glycol (mol. wt. 200)                                                                  2%                                                      kaolin                94%                                                     ______________________________________                                    

The finely ground active ingredient is uniformly applied, in a mixer, tothe kaolin moistened with polyethylene glycol. Non-dusty coatedgranulates are obtained in this manner.

    ______________________________________                                        (f) Suspension concentrates                                                                         (a)      (b)                                            ______________________________________                                        compound of Tables 1 to 4                                                                           40%      5%                                             ethylene glycol       10%      10%                                            nonylphenol polyethylene glycol ether                                                                6%      1%                                             (15 moles of ethylene oxide)                                                  sodium lignosulfonate 10%      5%                                             carboxymethylcellulose                                                                               1%      1%                                             37% aqueous formaldehyde solution                                                                     0.2%     0.2%                                         silicone oil in the form of a 75%                                                                     0.8%     0.8%                                         aqueous emulsion                                                              water                 32%      77%                                            ______________________________________                                    

The finely ground active ingredient is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of anydesired concentration can be obtained by dilution with water.

    ______________________________________                                        (g) Salt solution                                                             ______________________________________                                        compound of Tables 1 to 4                                                                            5%                                                     isopropylamine         1%                                                     octylphenol polyethylene glycol ether                                                                3%                                                     (78 moles of ethylene oxide)                                                  water                  91%                                                    ______________________________________                                    

BIOLOGICAL EXAMPLES EXAMPLE 3 Preemergence herbicidal action

In a greenhouse, immediately after sowing the test plants in seeddishes, the surface of the soil is treated with an aqueous dispersion ofthe test compounds, obtained from a 25% emulsifiable concentrate.Concentration ranges from 60 to 4000 g of test compound per hectare areapplied. The seed dishes are kept in the greenhouse at 22°-25° C. and50-70% relative humidity and the test is evaluated 3 weeks later. Thestate of the plants is assessed in accordance with the following rating:

1: plant has died or it has not germinated

2-3: very severe damage

4: severe damage

5: moderate damage

6: damage, the plant can recuperate

7-8: slight damage

9: normal growth, as untreated plants

The compounds of tables 1 to 4 that were tested showed strong herbicidalaction. The results obtained with compound 1.027 are summarized in Table5.

                  TABLE 5                                                         ______________________________________                                                   application rate                                                               g/ha                                                              Plant        2000     1000   300    250  125                                  ______________________________________                                        barley       9        9      9      9    9                                    wheat        8        9      9      9    9                                    maize        7        8      9      9    9                                    sorghum      7        7      9      9    9                                    soya-bean    9        9      9      9    9                                    sun-flower   7        8      9      9    9                                    Abutilon     1        1      4      4    5                                    Sida spinosa 1        1      4      4    5                                    Amaranthus sp.                                                                             1        1      1      1    1                                    Chenopodium sp.                                                                            1        1      1      1    1                                    Solanum nigrum                                                                             1        1      1      1    1                                    Chrysanthemum leuc.                                                                        1        1      1      1    1                                    Viola tricolor                                                                             1        1      1      1    1                                    Veronica sp. 1        1      1      1    1                                    ______________________________________                                    

EXAMPLE 4 Postemergence herbicidal action (selective weed control incereal)

Barley, wheat, maize and a number of weeds, are sprayed postemergence inthe 4- to 6-leaf stage with an aqueous active ingredient dispersion atrates of 60 to 2000 g of test compound per hectare and kept at 24°-26°C. and 45-60% relative humidity. The test is evaluated 15 days later inaccordance with the rating indicated above. The compounds of tables 1 to4 that were tested showed good herbicidal action. Some results are shownin Tables 6 and 7.

                  TABLE 6                                                         ______________________________________                                        application rate 1000 g/ha                                                    ______________________________________                                                  compound No.                                                        Plant       1.002  1.003  1.005                                                                              1.006                                                                              1.011                                                                              1.014                                                                              1.020                           ______________________________________                                        barley      6      6      7    8    6    8    7                               wheat       7      7      8    8    7    9    7                               Abutilon    1      1      1    1    1    1    1                               Sida spinosa                                                                              1      2      1    1    4    4    1                               Chenopodium sp.                                                                           2      3      1    1    2    4    1                               Solanum nigrum                                                                            1      1      1    1    1    1    1                               Ipomoea purp.                                                                             1      1      1    1    1    1    1                               Sinapis album                                                                             1      1      1    2    1    3    1                               Chrysanthemum                                                                             1      1      1    1    1    1    1                               leuc.                                                                         Galium aparine                                                                            3      1      1    4    4    2    2                               Viola tricolor                                                                            3      1      1    1    1    1    1                               Veronica sp.                                                                              1      1      1    1    1    1    1                               ______________________________________                                                  compound No.                                                        Plant       1.021  1.023   1.027                                                                              1.122 1.123                                                                              4.021                              ______________________________________                                        barley      7      6       8    7     6    6                                  wheat       6      7       8    7     6    7                                  Abutilon    1      1       1    1     1    1                                  Sida spinosa                                                                              1      1       4    1     1    1                                  Chenopodium sp.                                                                           1      1       2    1     1    1                                  Solanum nigrum                                                                            1      1       1    1     1    1                                  Ipomoea purp.                                                                             1      1       2    1     1    1                                  Sinapis album                                                                             1      1       1    1     1    4                                  Chrysanthemum                                                                             1      1       1    1     1    1                                  leuc.                                                                         Galium aparine                                                                            2      1       3    4     4    4                                  Viola tricolor                                                                            2      1       1    1     1    1                                  Veronica sp.                                                                              1      4       3    1     1    1                                  ______________________________________                                    

                  TABLE 7                                                         ______________________________________                                        application rate 250 g/ha                                                     ______________________________________                                                  compound No.                                                        Plant       1.002  1.003  1.005                                                                              1.006                                                                              1.011                                                                              1.014                                                                              1.020                           ______________________________________                                        barley      8      8      8    9    8    8    8                               wheat       8      9      9    9    9    9    8                               maize       6      6      8    7    6    7    6                               Abutilon    2      1      1    1    1    1    1                               Sida spinosa                                                                              3      3      4    4    4    4    3                               Chenopodium sp.                                                                           3      4      4    4    3    4    2                               Solanum nigrum                                                                            1      1      2    1    1    1    1                               Ipomoea purp.                                                                             1      1      1    1    1    1    1                               Sinapis album                                                                             3      2      1    2    3    3    5                               Chrysanthemum                                                                             2      1      1    2    1    1    2                               leuc.                                                                         Galium aparine                                                                            3      2      4    4    4    4    2                               Viola tricolor                                                                            4      1      1    1    3    1    4                               Veronica sp.                                                                              2      1      2    3    1    4    1                               ______________________________________                                                  compound No.                                                        Plant       1.021  1.023   1.027                                                                              1.122 1.123                                                                              4.021                              ______________________________________                                        barley      8      8       8    8     7    7                                  wheat       8      9       9    8     8    8                                  maize       7      7       8    6     6    6                                  Abutilon    1      1       3    1     1    1                                  Sida spinosa                                                                              3      4       5    1     1    1                                  Chenopodium sp.                                                                           3      1       3    4     1    1                                  Solanum nigrum                                                                            1      1       1    1     1    1                                  Ipomoea purp.                                                                             1      1       2    1     1    1                                  Sinapis album                                                                             4      2       1    1     2    4                                  Chrysanthemum                                                                             2      2       1    1     1    1                                  leuc.                                                                         Galium aparine                                                                            2      4       4    4     4    4                                  Viola tricolor                                                                            3      3       1    1     1    1                                  Veronica sp.                                                                              2      4       4    1     1    1                                  ______________________________________                                    

EXAMPLE 5 Selective herbicidal action in soya-beans

Soya-beans, grasses and weeds are reared in the greenhouse until theyhave reached after about 2 weeks the 4-leaf-stage. Then they are sprayedwith a diluted broth of active substance. The treated plants are thenkept in the greenhouse under optimal conditions for growth i.e. 26°-28°C. temperature, 43-60% relative humidity and regular watering. The testis evaluated 21 days after the treatment and the condition of the plantsis assessed according to the rating given in example 3.

The compounds of tables 1 to 4 that were tested, showed tolerancetowards the soya-plants and damaged the weeds. Some results are shown inTables 8 and 9

                                      TABLE 8                                     __________________________________________________________________________    application rate 500 g/ha                                                                  compound No.                                                     Plant        1.002                                                                            1.003                                                                            1.011                                                                            1.020                                                                            1.021                                                                            1.023                                                                            1.122                                                                            4.021                                       __________________________________________________________________________    soya-bean    8  6  7  7  7  6  6  6                                           sorghum sp.  4  4  4  3  3  3  4  3                                           Lolium perenne                                                                             4  4  5  4  4  3  3  5                                           Echinochloa  4  4  4  5  5  3  4  4                                           Abutilon     1  1  1  1  1  1  1  1                                           Sida spinosa 3  2  4  1  2  1  1  1                                           Xanthium     3  1  1  2  4  3  3  4                                           Amaranthus ret.                                                                            2  4  4  2  2  1  1  4                                           Chenopodium sp.                                                                            2  3  2  2  1  1  1  1                                           Solanum nigrum                                                                             1  1  1  1  1  1  1  1                                           Ipomoea purp.                                                                              1  1  1  1  1  1  1  1                                           Sinapis album                                                                              1  2  2  4  3  1  1  4                                           Chrysanthemum leuc.                                                                        1  1  1  2  1  1  1  1                                           Galium aparine                                                                             3  2  4  2  2  4  3  4                                           Viola tricolor                                                                             3  1  1  2  2  1  1  2                                           Veronica sp. 1  1  1  1  2  1  1  4                                           __________________________________________________________________________

                                      TABLE 9                                     __________________________________________________________________________    application rate 125 g/ha                                                                compound No.                                                       Plant      1.003                                                                            1.005                                                                            1.006                                                                            1.011                                                                            1.014                                                                            1.023                                                                            1.122                                                                            1.123                                                                            4.021                                      __________________________________________________________________________    soya-bean  7  8  8  7  7  8  7  7  7                                          Abutilon   1  1  1  1  1  1  1  1  1                                          Xanthium   1  2  2  1  3  4  4  4  4                                          Solanum nigrum                                                                           1  2  2  1  2  1  3  1  1                                          Ipomoea purp.                                                                            1  1  1  1  2  1  1  1  1                                          Chrysanthemum leuc.                                                                      1  1  3  2  2  2  1  1  1                                          Galium aparine                                                                           2  4  4  4  4  4  4  4  4                                          Viola tricolor                                                                           1  2  1  3  2  4  1  1  2                                          Veronica sp.                                                                             1  4  4  3  4  4  1  1  4                                          __________________________________________________________________________

EXAMPLE 6 Preemergence herbicidal action

Plastic pots are filled with expanded vermiculite (density: 0.135 g/cm³; water-absorbing capacity: 0.565 l/l). After the non-adsorptivevermiculite has been saturated with an aqueous emulsion in deionisedwater which contains the test compound in a concentration of 70.8 ppm,seeds of the following plants are sown on the surface: Nasturtiumofficinalis, Agrostis tenuis, Stellaria media and Digitaria sanguinalis.The pots are then kept in a climatic chamber at 20° C., an illuminationof about 20 klux and a relative humidity of 70%. During the germinatingphase of 4 to 6 days, the pots are covered with lightpermeable materialand watered with deionised water to increase the local humidity. Afterthe 5th day, 0.5% of a commercial liquid fertiliser (Greenzit®) is addedto the water. The test is evaluated 12 days after sowing and the actionon the test plants is assessed. The tested compounds of Tables 1 to 4exhibit good to very good herbicidal activity.

EXAMPLE 7 Herbicidal action in rice (paddy rice)

Rice and the weeds Scirpus sp. and Monocharia vag., which occur inwater, are sown in plastic beakers (surface: 60 cm² ; volume: 500 ml).After sowing, the beakers are filled with water up to the surface of thesoil. 3 days after sowing, the water level is increased to slightlyabove the soil surface (3-5 mm). Application is effected 3 days aftersowing by spraying the beakers with an aqueous emulsion of the testcompounds. The rate of application corresponds to a concentration of 0.5kg of active ingredient per hectare (concentration of the spraymixture=550 l/ha). The beakers are then kept in the greenhouse underoptimum growth conditions for rice weeds, i.e. at 25°-30° C. and at highhumidity. The evaluation of the tests takes place 3 weeks afterapplication. The state of the plants is assessed in accordance with therating indicated above. The tested compounds of tables 1 to 4 showedgood herbicidal action on the weeds while being tolerant towards therice plants.

EXAMPLE 8 Desiccation and defoliation action

Cotton plants of the Deltapine variety are reared in earthen-ware potsin a greenhouse. After the capsules have formed, the plants are sprayedwith an aqueous formulation of compound No. 1 at rates of applicationcorresponding to 1.2, 0.6 and 0.3 kg/ha in field application. Untreatedplants act as controls. Evaluation of the test is made 3, 7 and 14 daysafter application of the active ingredient by determining the degree ofdefoliation (percentage of fallen leaves) and of desiccation (drying outof the leaves remaining on the plant).

In this test, plants treated with compounds of Tables 1 to 4 at rates ofapplication of 0.6 and 1.2 kg/ha are left after 7 days with only a fewdried out leaves (>80% defoliation and dessication).

EXAMPLE 9 Growth inhibition of grasses and clover

A mixture of grasses Poa, Festuca, Lolium, Bromus, Cynosurus and ofclover (Trifolium pratense and repens) are sown in 15 cm plastic potsfilled with sterile garden soil and reared in a greenhouse at a daytemperature of 21° C. and a night temperature of 17° C. Lighting was13.5 hours daily at at least 7000 Lux. After emergence the plants werecut back each week to 6 cm hight. About 42 days after sowing and one dayafter the last cut, the plants are sprayed with an aqueous mixture of acompound of Tables 1 to 4 in an application between 0.3 and 3 kg/ha,which was prepared by dilution of a 25% wettable powder at an amount ofwater corresponding to 500 l/ha.

The test was evaluated 3 weeks after the treatment. The hight of theregrowth was measured and compared to the average regrowth of nottreated control plants. The compounds of Tables 1 to 4 that were testedreduced the regrowth by 10 to 80%.

We claim:
 1. A 5-(pyrazol-1-yl)-benzoic acid-thiol ester of the formulaI ##STR34## wherein X is hydrogen or halogen,Y is C₁ -C₄ alkyl X and Ytogether with the carbon atoms, to which they are bound, form also a 5-to 6-membered ring, which can be substituted by methyl Z is halogen, C₁-C₆ alkyl, C₁ -C₄ alkoxy or C₁ -C₄ alkylthio R₁ is hydrogen or halogen,R₂ is halogen, A is a straight chain or branched C₁ -C₄ alkylene bridge,which is unsubstituted or mono- or polysubstituted by C₁ -C₄ alkoxy, C₁-C₄ alkylthio or cyano.
 2. A5-[2-(4,5,6,7-tetrahydro-2H-indazolyl)]-benzoic acid-thiolesteraccording to claim 1 of the formula ##STR35## wherein A, R₁, R₂ and Zhave the meaning given in claim
 1. 3.5-[2-(3-Chloro-4,5,6,7-tetrahydro-2H-indazolyl)]-2-chloro-4-fluorobenzoicacid-(trimethylsilylmethylthio)ester according to claim
 1. 4. Aherbicidal and plant-growth-regulating composition, which contains,beside inert carrier material and other additives as active component, aherbicidally and growth-regulating effective amount of a5-(pyrazol-1-yl)-benzoic acid-thiolester according to claim
 1. 5. Amethod for controlling in pre- or postemergent application, weeds incrops of culture plants, which comprises treating the culture plant orthe crop area, with an effective amount of a compound according to claim1, or with a composition containing such a compound.
 6. A method for thedesiccation and defoliation of crops of cotton and potatoes, in order tofacilitate mechanical harvest, which comprises treating the culture,shortly before harvest, with an effective amount of a compound accordingto claim 1, or with a composition containing such a compound.